KR20090128886A - Method of preparing dichloropropanol from glycerol in the presence of heteropolyacid catalyst and/or absorbent under solvent-free conditions - Google Patents

Abstract

PURPOSE: A method for preparing dichloropropanol is provided to manufacture dichloropropanol from glycerol, not to need solvent removal, to reduce the volume of a reactor, and to efficiently process glycerol generated in a biodiesel manufacturing process. CONSTITUTION: A method for preparing dichloropropanol comprises a step of reacting glycerol with a chlorinating agent in the presence of at least one of a heteropolyacid catalyst and absorbent in a solvent-free condition. The absorbent comprises silica gel. The heteropolyacid catalyst is a Keggin type heteropolyacid catalyst with an atomic ratio of central element to coordinate element of 1:12.

Description

Method of preparing dichloropropanol from glycerol in the presence of heteropolyacid catalyst and / or absorbent under solvent-free conditions

The present invention relates to a process for preparing dichloropropanol from glycerol, and more particularly to a process for preparing dichloropropanol from glycerol in the absence of a solvent and in the presence of a heteropolyacid catalyst and / or absorbent.

Currently bio-diesel has been developed and produced competitively all over the world, and has already begun production in Korea and is commercially available as an additive material for diesel oil.

In the production of such biodiesel, a huge amount of glycerol, which is about 10% of the biodiesel production, is produced. However, since such glycerol is excessively supplied due to excessive supply compared to demand, it is desirable to achieve high value of glycerol by converting it to dichloropropanol having high added value.

Meanwhile, dichloropropanol is a raw material for producing epichlorohydrin, and epichlorohydrin is a raw material for epoxy resin, synthetic glycerin, ion exchange resin, flame retardant, solvent, medicine, dye, etc. Used. Most of the dichloropropanol currently supplied to the market is made from propylene. Specifically, the method for producing dichloropropanol is the step of preparing allyl chloride by high temperature chlorination of propylene and reacting allyl chloride and chlorine again using excess industrial water to produce dichloropropanol. Step (see US Patent 4,479,020, US Patent 6,051,742, US Patent 6,333,420). However, the production method of dichloropropanol using propylene has problems such as supply and demand instability due to the rising price of propylene, generation of a large amount of wastewater and waste, excessive initial investment costs due to the two-step manufacturing method, and difficulty in new expansion of the manufacturing method. Has

Accordingly, in recent years, a process of directly preparing dichloropropanol by a one-step manufacturing process in which glycerol is reacted with hydrochloric acid has secured economic feasibility. This one-step manufacturing method using glycerol can reduce the raw material cost by using inexpensive glycerol as a reactant, and can also significantly reduce the amount of wastewater and wastes by not using industrial water during the process. In addition, the process and environment-related investment costs are reduced, the initial investment costs are low. In addition, the production method using glycerol, unlike the conventional method for producing dichloropropanol through a two-step process from propylene, there is an environmentally friendly advantage by directly preparing dichloro propanol from glycerol as a biodiesel by-product.

In addition, when dichloropropanol is directly prepared by reacting glycerol with hydrochloric acid using a catalyst, it is possible to reduce costs and save energy through efficient catalyst development. Therefore, when developing an excellent catalytic process for producing dichloropropanol directly using glycerol, it is possible to preempt the environmental, economic and investment costs in the production of dichloropropanol and to secure technological competitiveness.

Currently, WO 2006/020234, WO 2005/054167 and WO 2005/021476 disclose a technique for producing dichloropropanol from glycerol by a continuous process using a carboxylic acid series homogeneous catalyst and using hydrogen chloride gas as the chlorinating agent. Doing.

In addition, Chinese Patent Publication No. 101007751A uses a nitrile catalyst to perform a one-step reaction in a Plug Flow Reactor, and continuously waters in a two-step reaction using a bubble cap tray. Disclosed is a technique for preparing dichloropropanol while reducing the consumption of hydrogen chloride gas.

In addition, Isu Chemical Co., Ltd. has a technology for producing dichloropropanol by mixing and diluting glycerol with a solvent without using a catalyst, and then reacting the diluted glycerol with a hydrogen chloride gas through a packed bed filled with glass beads. (See Korean Patent Publication No. 2008-0038284).

However, few patents have been reported on reactions and processes for the direct preparation of dichloropropanol from glycerol except for some of the patents described above. In particular, examples of direct preparation of dichloropropanol from glycerol using a heteropolyacid catalyst and / or absorbent in the absence of solvent have not been reported in the literature at all. Therefore, the present invention is original in this respect.

The present invention aims to provide a process for producing dichloropropanol from glycerol in high yield in the absence of solvents and in the presence of heteropolyacid catalysts and / or absorbents.

Another object of the present invention is to provide a method for preparing dichloropropanol which can simplify the process and reduce the production cost.

It is still another object of the present invention to provide a method for preparing dichloropropanol, which is free from azeotropic mixtures of catalysts and reaction products, facilitates catalyst recovery, and enables catalyst regeneration.

Still another object of the present invention is to provide a method for preparing dichloropropanol, which can efficiently treat glycerol generated in a biodiesel manufacturing process and achieve high value of glycerol.

The present invention to solve the above problems,

A method for preparing dichloropropanol by reacting glycerol with a chlorinating agent, the method providing a process for producing dichloropropanol, wherein the reaction proceeds in the absence of a solvent and in the presence of at least one of a heteropolyacid catalyst and an absorbent.

According to one embodiment of the invention, the absorbent comprises silica gel.

According to another embodiment of the present invention, the heteropolyacid catalyst is a Keggin type heteropolyacid catalyst having an atomic ratio of 1: 12 of a central element: isotope.

According to another embodiment of the present invention, the Keggin-type heteropolyacid catalyst, a plurality of hydrogen atoms in _12- molybdo tungstophosphoric acid (H ₃ PMo _12-X W _X O ₄₀ ) is substituted with a metal At least one heteropolyacid selected from species of heteropolyacids, wherein X = 0-12 in the formula.

According to another embodiment of the invention, the heteropolyacid catalyst is recovered after the reaction and reused.

According to another embodiment of the invention, the chlorinating agent is hydrogen chloride gas or hydrochloric acid.

According to another embodiment of the invention, the reaction is carried out in a batch reactor, a semi-batch reactor or a continuous stirring tank reactor (CSTR).

According to another embodiment of the invention, the reaction is carried out under a stirring speed of 600 ~ 1,100rpm.

According to a preferred embodiment of the invention, the reaction proceeds at a temperature of 50 ~ 300 ℃.

According to a preferred embodiment of the invention, the reaction proceeds at a pressure of 0.1-30 bar.

According to a preferred embodiment of the invention, the reaction proceeds for 10 minutes to 50 hours.

In addition, the present invention to solve the above problems,

In the method for producing epichlorohydrin (ECH) by reacting glycerol with a chlorinating agent to produce dichloropropanol,

It provides a method for producing epichlorohydrin comprising a method for producing dichloropropanol according to any one of the above embodiments, or using dichloropropanol prepared by the method.

According to the present invention, a process can be provided which can produce dichloropropanol from glycerol in high yield in the absence of a solvent and in the presence of at least one of a heteropolyacid catalyst and an absorbent.

In addition, according to the present invention, there can be provided a method for producing dichloropropanol that can reduce the manufacturing cost by simplifying the process.

In addition, according to the present invention, there is no problem of separation of the azeotrope mixture of the catalyst and the reaction product, it is easy to recover the catalyst, it is possible to provide a method for producing a dichloropropanol catalyst regeneration.

According to the present invention, there can be provided a method for producing dichloropropanol, which can efficiently treat glycerol generated in the biodiesel manufacturing process and achieve high value-adding of glycerol.

Next, a method for preparing dichloropropanol according to a preferred embodiment of the present invention will be described in detail.

The process for the preparation of dichloropropanol according to the invention comprises the chlorination reaction of glycerol, wherein the reaction proceeds in a reaction media-free state and in the presence of a heteropolyacid catalyst and / or an absorbent.

Hydrogen chloride gas or hydrochloric acid may be used as the chlorinating agent used in the chlorination reaction, but the present invention is not limited thereto.

The solvent is to uniformly disperse the glycerol to increase the contact area of the glycerol and the chlorinating agent, etc. In the past, it was common to use such a solvent in the preparation of dichloropropanol. However, in the method for preparing dichloropropanol according to the present invention, the contact area of glycerol and a chlorinating agent can be increased even in the absence of a solvent by maintaining a high stirring speed of the reaction mixture at 600 to 1,100 rpm. If the stirring speed is less than 600 rpm, complete mixing between glycerol and a chlorinating agent is not performed, and thus the contact activity between them is reduced, thereby lowering the reaction activity. On the other hand, when the stirring speed exceeds 1,100rpm, the effect of increasing the reaction activity according to the stirring speed increases is insignificant.

As described above, rapid stirring of the reactants is essential in the absence of a solvent and to prepare dichloropropanol, and therefore, the reaction may be performed in a batch reactor, a semi-batch reactor, or a constant stirred tank reactor. preferably in a tank reactor (CSTR). In addition, the reactor may be a reactor including an internal component formed of or coated with a material resistant to the chlorinating agent. Materials that are resistant to chlorinating agents include Hastelloy C or Teflon.

In this embodiment, the chlorination reaction is generally carried out at a temperature of 50 ~ 300 ℃, preferably 100 ~ 200 ℃. If the reaction temperature is less than 50 ℃ is not preferable in terms of the reaction rate, if it exceeds 300 ℃ is not preferable in terms of energy loss. In addition, the chlorination reaction is generally carried out in a pressure range of 0.1 ~ 30bar, in particular 1 ~ 15bar. The higher the reaction pressure, the better the activity, but when the predetermined pressure (30bar) is exceeded, there is no significant difference in the reaction activity. The reaction pressure is controlled by the pressure of the chlorinating agent. The reaction time is generally 10 minutes to 50 hours, preferably 1 hour to 20 hours. If the reaction time is less than 10 minutes, the conversion rate of glycerol is not low, it is not preferable, and if it exceeds 50 hours, the reaction is almost complete, there is no change in conversion or yield. In the present invention, "dichloropropanol" means a mixture of isomers consisting of 1,3-dichloropropan-2-ol and 1,2-dichloropropan-3-ol. In the method for preparing dichloropropanol according to the present embodiment, 1,3-dichloropropan-2ol is mainly produced, which material is particularly suitable as a reactant for epichlorohydrin preparation.

The chlorination reaction may proceed in the absence of solvent and in the absence of catalyst, but more preferably in the absence of solvent and in the presence of a heteropolyacid catalyst. When the reaction proceeds in the presence of a heteropolyacid catalyst, the reaction activity is increased so that the conversion of glycerol and the yield and selectivity of dichloropropanol can be increased than in the case without catalyst.

The heteropolyacid catalyst may be used for homogeneous or heterogeneous catalysis.

 The heteropolyacid catalyst includes a Keggin-type heteropolyacid having an atomic ratio of central element: isotope of 1:12.

The Keggin type heteropolyacid catalyst may include at least one heteropolyacid selected from a plurality of heteropolyacids in which all or a part of hydrogen atoms of _12- molybdoungstophosphoric acid (H ₃ PMo _12-X W _X O ₄₀ ) is substituted with a metal. And a number of X = 0 to 12 in the above formulas. The metal may include cesium (Cs) or silver (Ag).

As described above, the heteropolyacid catalyst substituted with a metal such as cesium or silver forms a three-dimensional structure which is insoluble in water and has a surface area of 40 m ² / g or more. As such, when an insoluble heteropolyacid catalyst forming a three-dimensional structure is used, the reaction can be performed in a heterogeneous process.

In addition, the heteropolyacid catalyst may be recovered after the reaction and reused. That is, the solid product may be recovered by evaporating the liquid product after the reaction, and the solid product may be recycled by being introduced into the reactor. The reason why the heteropolyacid catalyst can be recovered and reused after the reaction is that the mixed solution containing the heteropolyacid catalyst and the reaction product after the reaction does not form an azeotrope. When the mixed solution forms an azeotrope as in the case of using a conventional carboxylic acid-based catalyst, the liquid phase and the gas phase are in equilibrium, and the component ratio is constant and the boiling point does not change. There is a problem that is difficult to separate the catalyst from.

The addition of catalyst in a batch reactor, semi-batch reactor or continuous stir tank reactor (CSTR) can be carried out in a continuous or discontinuous manner.

The chlorination reaction may proceed in the presence of an absorbent or may proceed without an absorbent. That is, the chlorination reaction can be carried out in (i) a solvent-free, catalyst-free and absorbent state, (ii) a solvent-free and absorbent-free state, and in the presence of a heteropolyacid catalyst, and (iii) solvent-free and solvent-free. It may proceed in the catalytic state and in the presence of an absorbent, and (iv) in the absence of a solvent and in the presence of a heteropolyacid catalyst and an absorbent. Most preferred is the case of (iv) above. In the case where the reaction proceeds in the presence of an absorbent, the absorbent absorbs and removes water in the reaction mixture so that the conversion of glycerol and the yield and selectivity of dichloropropanol can be increased than in the case of the nonabsorbent state. The water is preferably removed as it is a byproduct of the reaction, which serves to hinder the production of additional dichloropropanol.

When the chlorination reaction is carried out in the presence of an absorbent, the absorbent may comprise silica gel, in particular silica gel blue.

In the reaction for producing dichloropropanol directly from glycerol in the absence of solvent, the conversion rate of glycerol, the selectivity of dichloropropanol, and the yield of dichloropropanol are calculated by the following Equations 1 to 3, respectively.

Selectivity of dichloropropanol is calculated based on a mixture of isomers consisting of 1,3-dichloropropan-2-ol and 1,2-dichloropropan-3-ol.

On the other hand, it may also be provided a method for producing epichlorohydrin comprising a method for producing dichloropropanol having the above configuration or using a dichloropropanol prepared by the above method. Specifically, a method for preparing epichlorohydrin from glycerol using a heteropolyacid catalyst may be represented by the following Chemical Formula 1.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example

Experimental Example  One: Solvent free , No catalyst  And Absorbent  Under conditions, from glycerol and hydrogen chloride gas Dichloropropanol  In the production of the reactor Stirring speed (RPM)  According Dichloropropanol  Reaction activity in manufacturing

Dichloropropanol was prepared directly from glycerol and 99.7 vol.% Hydrogen chloride gas in the absence of solvents, catalyst-free and absorbents. The reaction was in the liquid phase in a batch reactor with a volume of 200 ml and complete removal of water. The internal components of the batch reactor were formed from Hastelloy C and Teflon, materials that are resistant to chlorinating agents. First, only 100 g of glycerol was added to the batch reactor. Thereafter, the reaction temperature was fixed at 120 ° C., and the reaction was allowed to proceed for 3 hours while continuously introducing 99.7 vol.% Of hydrogen chloride gas, a chlorinating agent, into the batch reactor at a constant pressure of 3 bar. After completion of the reaction, the temperature of the reactor was cooled to room temperature, and then the product was analyzed using gas chromatography. In addition, the conversion ratio of glycerol, the selectivity of dichloropropanol and the yield of dichloropropanol were respectively calculated by Equations 1 to 3, and the results are shown in Table 1 below. As used in Table 1 below, "MCPD" and "DCP" mean monochloropropanediol and dichloropropanol, respectively.

Referring to Table 1, in the low stirring speed region of less than 600 RPM, due to mass transfer resistance, the reaction activity was greatly changed as the stirring speed was changed due to insufficient mixing of the reactants. However, in the high agitation speed range of 600 RPM or more, sufficient mass transfer occurred to show no significant change in the yield of dichloropropanol. Therefore, in all subsequent examples, the reaction experiment was carried out with the stirring speed of the reaction mixture fixed at 900 RPM in order to exclude the influence of mass transfer resistance.

Experimental Example  2: Solvent free , No catalyst  And Absorbent  Under conditions, from glycerol and hydrogen chloride gas Dichloropropanol  According to the change of reaction conditions (reaction temperature, reaction pressure, reaction time) Dichloropropanol  Reaction activity in manufacturing

Dichloropropanol was prepared in the same manner as in Experimental Example 1, except that the reaction was performed by changing the reaction temperature, the reaction pressure, and the reaction time as shown in Table 2 below. After completion of the reaction, the product was analyzed using gas chromatography. In addition, the conversion ratio of glycerol, the selectivity of dichloropropanol and the yield of dichloropropanol were calculated by Equations 1 to 3, respectively, and the results are shown in Table 2 below.

Referring to Table 2, by comparing the Experimental Examples 2-1 and 2-5, Experimental Examples 2-2 and 2-3, and Experimental Examples 2-4 and 2-6, respectively, the effect of the reaction temperature, Experimental Example By comparing 2-3 and 2-4, the effect of reaction pressure can be seen by comparing Experimental Examples 2-1 and 2-2, and Experimental Examples 2-6 and 2-7. As a result, the selectivity and yield of dichloropropanol increased with increasing reaction time under high temperature and high pressure. From the results in Table 2, it can be seen that a high yield of dichloropropanol can be obtained by appropriately controlling the reaction temperature, reaction pressure, and / or reaction time. As a representative example, when the reaction was carried out for 20 hours while maintaining a pressure of 5 bar at a relatively low temperature of 110 ° C. (Experimental Example 2-8), the yield of dichloropropanol was very high as 96.4%. This can be achieved by increasing the reaction time instead of reducing

Example  One: Solvent free  And Absorbent  State, and 12-molybdate tungstic acid ( H ₃ PMo _{12 -X} W _X O ₄₀ ) From glycerol and hydrogen chloride gas in the presence of a catalyst Dichloropropanol  According to the type of catalyst Dichloropropanol  Reaction activity in manufacturing

5 g of each of 5 catalysts in the form of H ₃ PMo _12-X W _X O ₄₀ (X = 0, 3, 6, 9, 12) as a heteropolyacid catalyst together with 100 g of glycerol was added to the batch reactor and the reaction temperature was decreased. Except that fixed at 110 ℃, dichloropropanol was prepared in the same manner as in Experimental Example 1. After completion of the reaction, the product was analyzed using gas chromatography. In addition, the conversion ratio of glycerol, the selectivity of dichloropropanol and the yield of dichloropropanol were respectively calculated by Equations 1 to 3, and the results are shown in Table 3 below. In addition, the analytical data of Experimental Example 2-2 was included in Table 3 for comparison.

Referring to Table 3, when the other conditions are the same, the reaction activity was higher when the heteropolyacid catalyst was used than the non-catalytic reaction, and the content of tungsten (W) (ie, the number of atoms of tungsten) increased as an isotope. It was found that the yield of dichloropropanol increased. Among the Keggin type heteropolyacid catalysts used, 12-tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ ) catalyst was found to be most effective for this reaction. The reaction proceeded in the presence of 12-tungstophosphoric acid catalyst showed a dichloropropanol yield in the absence of a catalyst and at least about 34% higher than the progressed reaction. This means that the use of a heteropolyacid catalyst in the reaction for producing dichloropropanol from glycerol and hydrogen chloride gas without solvent can achieve a greater effect than the case without catalyst.

Example  2: Solvent free  Under conditions and Dichloropropanol  In direct preparation, heteropolyacid catalysts (12- Molybdo tungstophosphate , H ₃ PMo _{12 - X} W _X O ₄₀ ) And / or reaction activity in the preparation of dichloropropanol with the presence of an absorbent (silica gel blue)

In one embodiment, together with 100 g of glycerol, 5 g of silica gel blue (SAMCHUN PURE CHEMICAL CO., LTD. / Silicagel blue, medium glanular, 5-10 mesh) was added to the batch reactor, except that the reaction temperature was fixed at 110 ° C. Was prepared in the same manner as in Experimental Example 1 dichloropropanol.

In another embodiment, dichloropropanol was prepared in the same manner as in Experimental Example 1, except that 5 g of H ₃ PW ₁₂ O ₄₀ as a heteropolyacid catalyst was added to a batch reactor together with 100 g of glycerol and the reaction temperature was fixed at 110 ° C. It was.

In another example, with 100 g of glycerol, 2.5 g of silica gel blue (SAMCHUN PURE CHEMICAL CO., LTD. / Silicagel blue, medium glanular, 5-10 mesh) as absorbent and 5 g of H ₃ PW ₁₂ O ₄₀ as a heteropolyacid catalyst were carried out in a batch reactor. Dichloropropanol was prepared in the same manner as in Experimental Example 1, except that the reaction temperature was fixed at 110 ° C.

After each reaction was completed, the product was analyzed using gas chromatography. In addition, the conversion rate of glycerol, the selectivity of dichloropropanol and the yield of dichloropropanol were respectively calculated by Equations 1 to 3, and the results are shown in Table 4 below. In addition, the analytical data of Experimental Example 2-2 was included in Table 4 for comparison.

Referring to Table 4, it can be seen that the yield of dichloropropanol was greatly improved even when only silica gel blue was added in addition to glycerol. This seems to be because the water produced in the reaction was absorbed and removed by silica gel blue. As in Example 1, the yield of dichloropropanol was greatly increased even when only H ₃ PW ₁₂ O ₄₀ catalyst was added in addition to glycerol. On the other hand, when silica gel blue and H ₃ PW ₁₂ O ₄₀ catalyst were added together in addition to glycerol, the effect of water removal by silica gel blue and the catalytic action of H ₃ PW ₁₂ O ₄₀ resulted in synergism, resulting in a dichloropropanol yield of silica gel blue or The rise was even greater than when only H ₃ PW ₁₂ O ₄₀ catalyst was used.

Evaluation example

Evaluation example  One: Solvent free , No catalyst  And Absorbent  Under conditions, from glycerol and hydrogen chloride gas Dichloropropanol  In the preparation of the reaction mixture Stirring speed (RPM)  DCP yield change according to Experimental Example 1

In each case where dichloropropanol was prepared from glycerol under the solvent-free, catalyst-free and absorbent-free state of Experimental Example 1, the yield (%) of dichloropropanol was graphically shown in FIG. 1.

Referring to FIG. 1, it can be seen that the DCP yield is greatly changed based on the case where the stirring speed of the reaction mixture is 600 RPM. In addition, it can be seen that the stirring speed should be at least 600 RPM in view of the DCP yield in this evaluation example.

Evaluation example  2: the central element is phosphorus (P) and tungsten (W) and / or molybdenum ( Mo ) By default Coordinated Keggin brother Heteropolyacid  In the catalyst An islet  Changes in DCP Yield According to the Number of Heavy Tungsten (W) Atoms (Example 1)

The yield (%) of dichloropropanol in each case where dichloropropanol was prepared from glycerol in the solvent-free and absorbent-free state of Example 1 and in the presence of a heteropolyacid catalyst was shown graphically in FIG. 2.

Referring to FIG. 2, the DCP yield increased as the number of tungsten (W) atoms in the heteropolyacid catalyst increased. In addition, in this evaluation example, the most preferred catalyst in terms of DCP yield was found to be 12- tungstophosphoric acid.

The method for producing dichloropropanol according to the present invention having the above constitution can directly prepare dichloropropanol from glycerol in the absence of a solvent and in the presence of a heteropolyacid catalyst and / or an absorbent. In addition, since the solvent is not used, a process for removing it after the reaction is unnecessary, and the reactor volume can be reduced. In addition, existing problems such as catalyst recovery and separation of the catalyst and reaction product azeotrope can be overcome. In this case, catalyst recovery and regeneration are easy to simplify the process, as well as to produce expensive dichloropropanol from low-cost glycerol in high yield.

Although preferred embodiments of the present invention have been described above with reference to the drawings and embodiments, these are merely exemplary, and various modifications and equivalent other embodiments are possible to those skilled in the art. You will understand. Therefore, the protection scope of the present invention should be defined by the appended claims.

1 is a graph showing the change of DCP yield according to the stirring speed (RPM) of the reaction mixture in the preparation of dichloropropanol from glycerol and hydrogen chloride gas under the solvent-free, catalyst-free and absorbent-free state (Experimental Example 1).

Figure 2 shows the change of DCP yield according to the number of tungsten (W) atoms in the isotope in the Keggin type heteropolyacid catalyst in which the central element is phosphorus (P) and the tungsten (W) and / or molybdenum (Mo) are basically coordinated It is a graph (Example 1).

Claims (12)

A process for preparing dichloropropanol by reacting glycerol with a chlorinating agent, wherein the reaction proceeds in the absence of a solvent and in the presence of at least one of a heteropolyacid catalyst and an absorbent. The method of claim 1, The absorbent is a method for producing dichloropropanol, characterized in that it comprises silica gel. The method of claim 1, The heteropolyacid catalyst is a method for producing dichloropropanol, characterized in that the Keggin-type heteropolyacid catalyst having an atomic ratio of central element: isotope of 1:12. The method of claim 3, The Keggin type heteropolyacid catalyst may include at least one heteropolyacid selected from a plurality of heteropolyacids in which all or a part of hydrogen atoms of _12- molybdoungstophosphoric acid (H ₃ PMo _12-X W _X O ₄₀ ) is substituted with a metal. Including, Method for producing dichloropropanol, characterized in that the number of X = 0 ~ 12 in the formula. The method of claim 1, The heteropolyacid catalyst is a method for producing dichloropropanol, characterized in that recovered after the reaction is reused. The method of claim 1, The chlorinating agent is a method of producing dichloropropanol, characterized in that the hydrogen chloride gas or hydrochloric acid. The method of claim 1, Process for producing dichloropropanol, characterized in that the reaction is carried out in a batch reactor, a semi-batch reactor or a continuous stirring tank reactor (CSTR). The method of claim 7, wherein Method for producing dichloropropanol, characterized in that the reaction proceeds under a stirring speed of 600 ~ 1,100rpm. The method of claim 7, wherein Method for producing dichloropropanol, characterized in that the reaction proceeds at a temperature of 50 ~ 300 ℃. The method of claim 7, wherein Method for producing dichloropropanol, characterized in that the reaction proceeds at a pressure of 0.1 ~ 30bar. The method of claim 7, wherein Method for producing dichloropropanol, characterized in that the reaction proceeds for 10 minutes to 50 hours. In the method for producing epichlorohydrin (ECH) by reacting glycerol with a chlorinating agent to produce dichloropropanol, A method for producing epichlorohydrin comprising the method for producing dichloropropanol according to any one of claims 1 to 11 or using dichloropropanol prepared by the method.

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